KR101824445B1 - Cleaning method and cleaning device used in said cleaning method - Google Patents

Abstract

The cleaning method of the present invention includes a cleaning step of cleaning the object to be cleaned and the cleaning step is an immersion step of immersing the object to be cleaned with the flux residue in a cleaning composition of a specific composition contained in a pressure adjustable cleaning tank (Second process) in which the pressure in the cleaning tank is P ₁ (kPa), the pressure in the cleaning tank depressurized in the depressurization process is set to P ₁ ± 0.4 (kPa) (A third step) in which the temperature of the cleaning tank is maintained at 50 to 70 DEG C for 8 to 16 seconds; a step-up step for raising the pressure in the cleaning tank to P ₂ (kPa) And the second to fourth steps are performed for 10 to 220 seconds.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning method for cleaning an object to be cleaned,

The present invention relates to a method of cleaning a to-be-cleaned object to which a flux residue is adhered, a method of manufacturing an electronic part using the method, and a cleaning apparatus used in the method.

Conventionally, as a detergent composition of a subject to be cleaned with a flux residue, a composition containing a glycol ether compound and an amine compound (see Patent Documents 1 and 2) and a composition further containing a surfactant Etc.) are known.

Further, a cleaning method for removing an abrasive attached to a wristwatch or the like, which is not a method for cleaning an object to be cleaned to which a flux residue is adhered, includes a cleaning method in which an operation of increasing the pressure around the cleaning liquid and an operation of decreasing the pressure around the cleaning liquid are alternately Patent Document 5) discloses a pressure swing cleaning method in which a reduced pressure and an atmospheric pressure are repeatedly applied to the inside of a liquid tank as a cleaning method for a component having a gap such as a fine closed hole (see Patent Document 6, etc.) .

In the cleaning method described in Patent Document 5, for example, a solvent naphtha-based cleaning liquid is used as the cleaning agent composition. In the cleaning method described in Patent Document 6, a dilution liquid of a surfactant is used as a detergent composition. After the interior of the liquid tank is depressurized to a desired pressure, the control valve is immediately switched to return the inside of the liquid tank to normal pressure.

Japanese Patent Application Laid-Open No. 9-87668 Japanese Patent Application Laid-Open No. 2009-41094 Japanese Patent Application Laid-Open No. 4-57897 Japanese Patent Application Laid-Open No. 3-227400 Japanese Patent Application Laid-Open No. 2001-170577 Japanese Patent Application Laid-Open No. 6-296940

When a component (for example, a semiconductor chip, a chip capacitor, another circuit board, or the like) is mounted on a circuit board in the process of manufacturing an electronic component such as a semiconductor device, a space is formed between the circuit board and the component . The solder used for mounting the component includes a flux. When the flux remains as a residue for a long period of time in the gap after soldering, migration may occur, which may cause a short circuit between the electrodes.

2. Description of the Related Art [0002] With miniaturization and high density of electronic components, a semiconductor chip mounting method using a solder bump such as a flip chip method is widely used, so that higher reliability is demanded for mounting. Therefore, the importance of flux residue cleaning in the manufacture of electronic components is further increased.

However, due to miniaturization and high density of electronic components, the gap is further narrowed. Flux residues entering such a narrow gap are difficult to remove, and as a result, there is a problem that the productivity of electronic parts is inferior. Therefore, it has been desired to develop a cleaning method with good removability of flux residues remaining in a narrow gap.

The present invention relates to a cleaning method of a cleaned object to which a flux residue is adhered, which has high cleaning property against a flux residue existing in a narrow gap, has good rinsability by water and suppresses bubbles, Of the present invention.

The cleaning method of the object to be cleaned with the flux residue of the present invention includes a cleaning step of cleaning the object to be cleaned with the flux residue using the cleaning agent composition. The cleaning step includes an immersion step (first step) of immersing the object to be cleaned with the flux residue in the cleaning composition contained in a pressure-adjustable cleaning tank, 1) with the pressure P ₁ (kPa) pressure step (second step), and said pressure P ₁ ± 0.4 in the cleaning tank (kPa) pressure in the pressure step of pressure by satisfying a, and the contained in the cleaning tank (3) holding the temperature of the detergent composition continuously at 50 to 70 DEG C for 8 to 16 seconds, and a pressure reducing step of maintaining the pressure in the cleaning tank after satisfying the following formula (2) (Fourth step) in which the pressure P ₂ (kPa) is set. The second to fourth steps are carried out for 10 to 220 seconds.

0.1 (kPa)? P _1? 7 (kPa) (1)

_{50 (kPa) ≤P 2 ≤120 (} kPa) (2)

The detergent composition comprises at least 2 wt% to 10 wt% of water (component A), at least 50 wt% to less than 97.75 wt% of glycol ether (component B), and at least 0.05 wt% to 5 wt% of amine compound (component C) .

The component B is represented by the following general formula (1).

R^One-O- (EO)_m-R² (One)

Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO is an oxyethylene group, m is an average addition mole number of EO, ? 3.

The component C is represented by the following general formula (2).

P and q each represent an average addition mole number of EO, and 1? P + q? 4 is an integer of 1 to ³ , and R < ³ > represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, EO represents an oxyethylene group, Satisfies.

The method for manufacturing an electronic component including the solder bump of the present invention includes the steps of forming a solder bump on a substrate of an electronic component by using a solder flux containing flux, And washing the flux residue derived from the flux.

The cleaning apparatus of the present invention is a cleaning apparatus used in a cleaning method of the object to be cleaned of the present invention,

And a moisture control mechanism for controlling the content of the water (component A) in the detergent composition in the cleaning tank to 2 wt% or more and 10 wt% or less.

Certain detergent compositions are used in the present invention. In addition, since a series of steps including the depressurization step, the depressurization step, and the step-up step are carried out in one cycle and this one cycle is carried out within a specified time, the physical force caused by the pressure change, The physical force generated due to the boiling of the composition acts on the flux residue existing in a narrow gap of the object to be cleaned. Therefore, there is a need for a cleaning method of a cleaning object to which a flux residue is adhered, in which not only the cleaning property of the flux residue existing in a narrow gap is high but also the rinsing property by water is good and the bubble is suppressed, And a method of manufacturing the electronic component.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a conceptual plan view of a test piece used for cleaning property evaluation of detergent compositions for flux residues. FIG.
Figure 1B is a conceptual side view of the test piece shown in Figure 1A.
2 is a schematic view of a pressure adjustable cleaning tank used in a forming test of a cleaning composition.
3 is a conceptual diagram of a cleaning apparatus used in the embodiment.

The term " flux "in the present invention refers to a rosin-based flux mainly containing rosin or rosin derivatives used for soldering, and in the present invention," soldering "includes reflow and flow soldering. In the present invention, "solder flux" refers to a mixture of solder and flux, and "flux residue" refers to a flux-derived residue remaining on a substrate after soldering using flux or solder flux. The term "solder" in the present invention also includes lead (Pb) -containing solder and Pb-free solder.

The term " physical force generated by the boiling of the detergent composition "in the present invention refers to the physical force due to convection generated by boiling water contained in the detergent composition, and" boiling of the detergent composition & It means boiling water. Therefore, the greater the water content in the detergent composition, the greater the physical force, and the smaller the water content in the detergent composition, the smaller the physical force.

In the cleaning method of the object to be cleaned with the flux residue of the present invention (hereinafter abbreviated simply as "cleaning method"), the water content is preferably not less than 2% by weight and not more than 10% By carrying out a series of processes including the depressurization step, the depressurization maintaining step and the pressure increasing step in this order within a predetermined time and securing the depressurized pressure holding time for a predetermined period of time by using the detergent composition having a specific surface area The cleaning property with respect to the flux residue remaining in the substrate is high, the bubbles are suppressed, and the rinsing property by water is good. When the above-described series of steps is carried out in one cycle, and when one cycle is repeatedly performed, the cleaning property against the flux residue existing in a narrow gap becomes higher. Therefore, when the cleaning method of the present invention is used in the manufacturing process of an electronic part including a solder bump, productivity and reliability of the electronic part can be expected to be improved.

[Cleaning method of the object to be cleaned]

In the cleaning method of the present invention, for example, a cleaning step, a rinsing step of rinsing the object to be cleaned with the rinsing composition, and a drying step are carried out in this order.

[Purified water]

The object to be cleaned to which the cleaning method of the present invention is preferably used is a manufacturing intermediate including a component soldered to a circuit board or the like and a circuit board and includes a flux residue in a gap between the circuit board and the component. The manufacturing intermediate is a manufacturing intermediate in a manufacturing process of an electronic component such as a semiconductor package or a semiconductor device. For example, a semiconductor chip, a chip-type capacitor, another circuit board, or the like is mounted on a circuit board by soldering using flux .

The clearance in the object to be cleaned is, for example, a space formed between the circuit board and the parts mounted by soldering on the circuit board, and the height (the shortest distance between the circuit board and the parts) is, for example, 5 to 500 Mu m, 10 to 250 mu m, or 20 to 100 mu m. The width and depth of the gap depend on the size or the interval of the electrodes (lands) on the parts to be mounted or the circuit board. For example, the width is 130 to 20,000 mu m or 130 to 10000 mu m, the depth is 130 to 25000 mu m, Lt; / RTI >

[Cleaning process]

The cleaning process includes an immersion process (the soaking process is referred to as a "first process") in which the object to be cleaned with the flux residue is immersed in a cleaning composition to be described later housed in a pressure adjustable cleaning bath, (The pressure reducing step is also referred to as a " second step ") in which the pressure in the cleaning tank is reduced to a predetermined pressure range, Pressure holding step (also referred to as a " third step ") of maintaining the pressure in the cleaning tank continuously for a predetermined period of time, Process is also referred to as "fourth process").

The cleaning step may further include a pressure holding step after the pressure increasing step (step 4a) and / or a fifth step. Step 4a is carried out after the fourth step, and if the cleaning step includes the fifth step, it is carried out before the fifth step. In the step 4a, the pressure in the cleaning tank is maintained within a predetermined pressure range for a predetermined time. The fifth step is performed after the fourth step, and if the cleaning step includes the step 4a, it is carried out after the step 4a. In the fifth step, a series of steps including at least the second to fourth steps are repeated one to fifty times.

In the cleaning method of the present invention, the cleaning step may be carried out using one cleaning tank or two or more cleaning tanks. For example, when the cleaning method of the present invention is carried out using one cleaning tank, the first step is not performed in the fifth step, and the second to fourth steps may be repeated one to fifty times. When the cleaning method of the present invention is carried out using two or more cleaning tanks, the first to fourth steps may be repeated 1 to 50 times in the fifth step, and the number of repetitions in the fifth step may be repeated X times , The first to fourth steps may be repeated Y (where Y <X) times, and the second to fourth steps may be repeated (XY) times.

In one example of the cleaning method of the present invention, the series of the steps from the second step to the fourth step, that is, the second step to the fourth step is carried out for 10 to 220 seconds, and the amount of the flux residue present in the narrow gap Preferably 15 to 100 seconds, more preferably 15 to 50 seconds, and more preferably 15 to 40 seconds, from the viewpoint of increasing the qualities and shortening the cleaning time.

(First step)

In the cleaning step, the object to be cleaned, to which the flux residue is adhered, is first introduced into the cleaning tank containing the detergent composition, and the object to be cleaned is immersed in the cleaning agent composition.

The filling amount of the detergent composition with respect to the cleaning tank is not particularly limited as long as the amount of the object to be cleaned is immersible.

As the cleaning tank, for example, a pressure resistant vessel provided with a heating means, an ultrasonic vibrator or the like can be used. The inside of the cleaning tank is communicated with an air pipe connected to a suction device such as a vacuum pump, and the air pipe includes a branch pipe not connected to the suction device. The inside of the cleaning tank can be depressurized or pressurized to a desired pressure by opening and closing control of the switching control valve provided in the branch pipe. An example of such a cleaning bath is disclosed in, for example, Japanese Patent Application Laid-Open No. 6-296940.

The temperature of the cleaning agent composition filled in the cleaning tank in the first step is preferably 50 to 70 캜, preferably 55 to 70 캜, and more preferably 60 to 70 캜 before the decompression starts, More preferable. Specifically, a cleaning agent composition adjusted to 10 to 40 DEG C is filled in the cleaning tank and heated to a temperature within the preferable range. Heating of the detergent composition may be carried out by using a heating means provided in the cleaning tank, if necessary. The temperature of the cleaning composition is measured with a thermometer installed in the cleaning bath.

(Second Step)

Next, the pressure is reduced until the pressure in the washing tank becomes P ₁ (kPa). P ₁ satisfies the relational expression 0.1 (kPa)? P _1? 7 (kPa).

In the second step, the inside of the cleaning tank is preferably 0.1 to 6 (kPa), more preferably 0.1 to 5 (kPa), from the viewpoint of improving the cleaning property against the flux residue present in a narrow gap of the object to be cleaned and shortening the cleaning time. (kPa), more preferably 0.1 to 4 (kPa).

In the second step, the detergent composition can be forcibly put into a narrow gap by the decompression, so that the air which interferes with the contact between the flux residue present in the narrow gap and the detergent composition can be driven out of the gap, Dissolved gas can also be degassed. Therefore, the cleaning method of the present invention is suitable as a method for cleaning a flux residue that enters a narrow gap.

From the viewpoint of both improving the cleaning property of the flux residue present in a narrow gap and shortening the cleaning time, it is preferable that the pressure reduction time required to make the pressure in the cleaning tank P ₁ (kPa) More preferably from 1 second to 120 seconds from the start of decompression, more preferably from 1 second to 60 seconds, even more preferably from 1 second to 30 seconds, further preferably from 1 second to 15 seconds Do.

In the second step, the decompression rate at which the pressure in the cleaning tank is set to P ₁ (kPa) is 15 to 30 (kPa / s) from the viewpoint of both improvement in cleaning property against flux residue present in a narrow gap and shortening of cleaning time More preferably 17 to 30 (kPa / s), and even more preferably 18 to 30 (kPa / s).

The temperature of the detergent composition in the second step is preferably from the viewpoint of improving the cleaning property against the flux residue present in a narrow gap, more specifically, from the viewpoint of obtaining a high physical force by boiling of the detergent composition and suppressing evaporation of water in the detergent composition Is preferably 50 to 70 ° C, more preferably 55 to 70 ° C, in the same manner as in the first step, from the viewpoint of suppressing the decrease in the water content in the cleaning bath, , More preferably 60 to 70 ° C. Heating of the detergent composition may be carried out by using a heating means provided in the cleaning tank, if necessary. That is, in the second step, it is preferable to maintain the temperature of the detergent composition adjusted to the temperature within the preferable range in the first step. The temperature of the cleaning agent composition in the second step is an average value of the temperature measured for example every one second by a thermometer provided in the cleaning tank. This average value can be obtained by a formula for calculating the average temperature of the detergent composition in the third step described later.

(Third step)

Next, in the depressurization maintaining step, the pressure in the depressurized depressurization tank is maintained at P _1. + -. 0.4 kPa, and the temperature of the detergent composition in the cleaning tank is maintained at 50 to 70 DEG C for 8 to 16 seconds.

In the third step, the pressure in the washing tank needs to be 0.1 to 7 (kPa) from the viewpoint of maintaining the stable boiling state of the detergent composition. From the same point of view, the variation width of the pressure in the washing tank in the third step is P ₁ ± 0.3 (kPa), more preferably P ₁ ± 0.2 (kPa), and even more preferably P ₁ ± 0.1 (kPa). That is, the pressure in the cleaning tank in the reduced pressure holding step is preferably substantially constant, and more preferably, constant. Meanwhile, the pressure in the washing tank is measured by a manometer.

The temperature of the cleaning agent composition in the third step is required to be 50 to 70 占 폚 when the pressure in the cleaning tank is P ₁占 0.4 (kPa) from the viewpoint of maintaining the stable boiling state of the cleaning agent composition. In the case where the pressure P _{1 in the} cleaning tank is 0.1 to 5 (kPa), it is preferably 50 to 70 ° C, and the pressure P _{1 in the} cleaning tank is more than 5 kPa And when it is 7 kPa or less, it is preferably 60 to 70 ° C.

The temperature of the detergent composition in the third step may be varied within a temperature range of 50 to 70 ° C and the fluctuation range may be set to be from the viewpoint of maintaining a stable boiling state of the detergent composition, It is preferably within ± 1.0 ° C, more preferably within ± 0.5 ° C, and even more preferably within ± 0.2 ° C. That is, in the cleaning method of the present invention, the temperature of the cleaning agent composition in the third step is preferably substantially constant, more preferably constant.

The temperature (Ti) of the cleaning agent composition in the third step is measured, for example, every one second by a thermometer provided in a washing tank. The average value (Tx) of the temperature of the detergent composition in the third step (time average holding temperature) can be obtained by the following formula.

Time average holding temperature Tx = Σ (Ti * t _i ) / Σt _i

[Let Ti be the holding temperature before the averaging and t _i hold the temperature at that temperature.]

The boiling state of the detergent composition needs to be 8 seconds or more from the viewpoint of improving the cleaning property against the flux residue present in the narrow gap in the third step. Further, from the viewpoint of both improving the cleaning property of the flux residues present in the gaps and shortening the cleaning time, it is required that the reduced pressure holding time (the time of the third step) be 16 seconds or less. Therefore, the decompression holding time is 8 to 16 seconds from the viewpoint of both improving cleaning property of the flux residue present in the gap and shortening of the cleaning time. For the same reason, 8 to 15 seconds is preferable, and 9 to 13 seconds is more preferable.

The reduced pressure holding time is calculated from the point of time when the pressure in the washing tank reaches P ₁ in the second step (depressurization step). When the pressure in the cleaning tank is reduced to 5 (kPa) in the second process, P ₁ is 5 (kPa). When the pressure in the cleaning tank reaches 5 (kPa) Time is measured. If the pressure in the cleaning tank is in the range of P ₁ ± 0.4 (kPa) even if the pressure in the cleaning tank is increased or decreased in the third process, the pressure in the cleaning tank is maintained in the reduced pressure state and the reduced pressure holding time is calculated.

The third step is preferably carried out while applying ultrasonic vibration to the cleaning composition. When the ultrasonic vibration is applied to the detergent composition after the dissolved gas in the detergent composition is degassed while satisfactorily contacting the flux residue with the detergent composition by moving the air present in the gap through the second process by passing through the second process, The detergency against existing flux residues is improved, and it is preferable because blast furnace can be expected to shorten the cleaning time.

The frequency of the ultrasonic waves and the energy density of the ultrasonic waves imparted to the detergent composition in the third step are preferably in the range of 20 to 400 kHz and 0.1 to 4.0 W / cm &lt; 2 &gt; in terms of suppressing the damage to the objects to be cleaned, More preferably 35 to 200 kHz and 0.2 to 2.0 W / cm &lt; 2 &gt;.

The application of the ultrasonic vibration can be performed, for example, by an ultrasonic vibrator disposed in the cleaning bath.

In the cleaning method of the present invention, the application of the ultrasonic vibration to the cleaning composition is not limited to the third step. The ultrasonic vibration imparting to the cleaning composition may be performed during at least one of the first to fifth steps. It is preferable that the ultrasonic vibration imparting to the cleaning composition is performed in all steps of the first to fifth steps from the viewpoint of improving the cleaning property against the flux residue present in the gap.

(Fourth step)

Next, the pressure is increased until the pressure in the washing tank becomes P ₂ (kPa). P ₂ satisfies the relationship 50≤P ₂ ≤120 (kPa).

In the fourth step, the pressure in the washing tank is preferably in the range of 50 to 102 kPa, more preferably in the range of 80 to 102 kPa, more preferably in the range of 80 to 102 kPa from the viewpoint of improving the cleaning property of the flux residue present in the gap, Is more preferable. On the other hand, the atmospheric pressure is the pressure when no decompression or pressure is applied, which is usually atmospheric pressure and is about 1 atm (101.3 (kPa)).

From the viewpoint of both improving the cleaning property of the flux residue present in a narrow gap and shortening the cleaning time, it is preferable that the pressure rising time required to make the pressure in the cleaning tank P ₂ (kPa) More preferably from 1 second to 60 seconds, more preferably from 1 second to 30 seconds, and still more preferably from 1 second to 10 seconds.

The temperature of the detergent composition in the fourth step is preferably the same as the temperature of the detergent composition in the third step from the viewpoint of improving the cleaning property against the flux residue present in a narrow gap, Deg.] C, and more specifically, the same temperature as the holding temperature in the third step. Heating of the detergent composition may be carried out using a heating means provided in the cleaning tank as necessary. The temperature of the cleaning agent composition in the fourth step is an average value of the temperature measured for example every one second by a thermometer provided in the cleaning tank. The average value can be obtained from the above-described calculation formula of the average temperature of the cleaning agent composition in the third step.

(Step 4a)

The cleaning method of the present invention is carried out before the fifth step described later after the fourth step and the pressure P ₃ in the cleaning tank is set to 50 to 120 (kPa) in view of enhancing the cleaning property against the flux residue present in the narrow gap. Pressure holding step (this step is also referred to as " step 4a ") in which the pressure is maintained within a range of P ₂ ± 0.4 (kPa) for 8 to 16 seconds. In particular, when the ultrasonic vibration is applied to the cleaning composition in the fourth step, the cleaning method of the present invention preferably includes the above-mentioned step 4a from the viewpoint of improving the cleaning property.

For example, when the pressure P ₂ (kPa) in the cleaning tank in the fourth step is lower than the normal pressure, the cleaning tank is opened to balance the internal pressure of the cleaning tank with the external pressure of the cleaning tank, Can be maintained for a predetermined time.

Claim that the three temperature of the detergent composition in the washing tub at 4a process of three when the pressure is P ₁ ± 0.4 (kPa) in the tank, particularly 50 ~ 70 ℃ in terms of efficiency at the time of the repeated washing in a third step desirable. The temperature of the cleaning agent composition in the cleaning tank in the step 4a may vary within a range of 50 to 70 占 폚, but it is more preferably the same as the temperature of the cleaning agent composition in the fourth step. The temperature of the detergent composition in the step 4a is an average value of the temperature measured for example every one second by a thermometer provided in the cleaning bath. The average value can be obtained from the above-described calculation formula of the average temperature of the cleaning agent composition in the third step.

The three pressure time keeping P ₃ at a pressure greater than P ₂ ± 0.4 (kPa) or or P ₂ ± 0.4 (kPa) in the range of 50 ~ 120kPa in a bath at 4a process three of the flux residues present in the gap It is preferably from 8 to 18 seconds, more preferably from 8 to 16 seconds, and even more preferably from 9 to 16 seconds from the viewpoint of both improving the qualities and shortening the cleaning time.

When the cleaning method of the present invention includes the step (4a), if the series of the steps from the second step to the step (4a) is made into one cycle, improvement of the cleaning property against the flux residue present in a narrow gap and shortening of the cleaning time From the viewpoint of compatibility, the above-mentioned one cycle is preferably carried out for 20 to 230 seconds, preferably 25 to 110 seconds, more preferably 25 to 60 seconds, and still more preferably 25 to 50 seconds .

(Step 5)

The cleaning method of the present invention preferably includes a step of repeating the above-mentioned second to fourth steps 1 to 50 times (fifth step) from the viewpoint of improving the cleaning property against the flux residue present in a narrow gap . The second to fourth steps repeatedly performed in the fifth step may be carried out under the same conditions as the second to fourth steps performed before the fifth step. Concretely, from the viewpoint of both improving the cleaning property of the flux residue present in the narrow gap and shortening the cleaning time, in the second step repeatedly carried out, the pressure in the cleaning tank is reached to the pressure within the range of 0.1 to 6 (kPa) The decompression time is preferably from 1 second to 120 seconds from the start of decompression, and the temperature of the detergent composition is preferably from 50 to 70 ° C. From the same viewpoint, it is preferable to maintain the pressure in the cleaning tank at a pressure of P ₁ ± 0.4 (kPa) in the third step repeatedly performed, and maintain the pressure in the cleaning tank at a pressure of P ₁ ± 0.1 (kPa) And the temperature of the detergent composition is preferably from 50 to 70 ° C when the pressure in the cleaning tank is P ₁ ± 0.4 (kPa), more preferably the temperature of the detergent composition is constant, To 16 seconds. From the same viewpoint, in the fourth step repeatedly carried out, the pressure reached by the pressure-rising is preferably atmospheric pressure, and the temperature of the detergent composition is preferably 50 to 70 ° C.

On the other hand, when the cleaning tank is changed every time the second to fourth steps are completed, it is necessary to further immerse the object to be cleaned in the cleaning agent composition (the first step). Therefore, To " the step of repeating 50 times more "can be understood as" the step of repeating the first to fourth steps 1 to 50 times more ". When the cleaning method of the present invention includes the step (4a), it is preferable to carry out the step (4a) after the fourth step in the fifth step. In the case where the fifth step includes the step 4a, it is preferable to carry out the step 4a after at least one repeated cycle when the second to fourth steps repeatedly carried out are made into one cycle, It is more preferable to carry out the step 4a after all the cycles in the fifth step from the viewpoint of both improving cleaning property and shortening the cleaning time for the flux residue present. That is, in the fifth step, it is preferable to repeat at least one cycle consisting of the second step to the fourth step from 1 to 50 times, and repeating one cycle consisting of the first step to the fourth step is repeated 1 to 50 times Or one cycle consisting of the second step to the fourth step is preferably repeated for 1 to 50 times.

Although the number of repetition times (the number of cycles in the fifth step) varies depending on the shape of the object to be cleaned and the state of the flux residue, it is preferably 1 to 40 times from the viewpoint of improving cleaning property and productivity of the flux residue present in the gap , More preferably 2 to 35 times, and still more preferably 3 to 30 times. By repeating the second to fourth steps, the first to fourth steps, or the second to fourth steps in a short time, the physical force generated by the pressure change and the physical force generated during the reduced pressure holding step The physical force generated due to boiling of the detergent composition is repeatedly added to the object to be cleaned. Therefore, the cleaning property of the flux residue existing in a narrow gap becomes higher.

(Adjustment of water content)

In the cleaning method of the present invention, water may be added to the cleaning agent composition in the cleaning tank during the cleaning step for cleaning one object to be cleaned. When the cleaning tank is continuously used to clean a plurality of objects to be cleaned, water may be added to the cleaning agent composition in the cleaning tank during and / or before the cleaning process for cleaning each object to be cleaned. In the cleaning method of the present invention, since the cleaning agent composition is boiled, the content of water in the cleaning agent composition may be reduced during repeatedly performing the second to fourth steps in the fifth step. Therefore, in order to suppress the fluctuation of the mixing ratio of each component in the detergent composition used in the present invention and to maintain the high cleaning property, the cleaning agent composition in the cleaning tank before and / or during any one of the first to fifth steps It is preferable to add water to suppress the compositional fluctuation of the detergent composition.

The concentration of water in the detergent composition before and / or during any one of the first to fifth steps is measured with a moisture meter such as a water sensor, and water is added to the detergent composition in the washing tank based on the measured value It can be spread. In order to accurately measure the concentration of water in the detergent composition, it is preferable that the concentration of water is measured while the detergent composition is stirred by a stirrer, a circulating pump, an ultrasonic vibrator or the like.

The detector type of the moisture sensor is not particularly limited, and may be, for example, a near-infrared spectroscopy type, a capacitive conductivity type, or a conductivity type.

The replenishment of the cleaning agent composition in the cleaning tank is carried out by, for example, circulating the cleaning agent composition in the cleaning tank in the sub tank, which is connected to the cleaning tank and has an electromagnetic valve that is opened or closed in accordance with the measured value by the moisture sensor provided in the cleaning tank, . When the cleaning tank is continuously used to clean a plurality of objects to be cleaned, the supply of water may be performed by, for example, raising the object to be cleaned from the cleaning tank to remove the object to be rinsed, It is preferable to carry out the water before the water is introduced into the washing tank. It is preferable that the water sensor is provided not only in the cleaning tank but also in the sub tank.

The adjustment of the water content in such a detergent composition can be carried out, for example, by using a cleaning device as shown in Fig.

As shown in FIG. 3, the cleaning apparatus includes a pressure adjusting unit (not shown) that allows the cleaning agent composition to be stored therein, adjusts the internal pressure thereof, and a cleaning agent composition A cleaning tank 11 including a water meter 15 capable of measuring the concentration of water and a sub tank 14 capable of storing the cleaning agent composition and a cleaning tank 11 capable of communicating the cleaning tank 11 and the sub tank 14 And a valve 17 (for example, a solenoid valve) for opening and closing the flow path in accordance with the measured value by the moisture meter 15, and a circulation conduit 18 for measuring by the moisture meter 15 (Pump or the like not shown) for circulating the detergent composition in the cleaning bath 11 and the cleaning agent composition in the sub tank 14 through the circulation line 18 according to the value of the cleaning liquid.

In the above cleaning apparatus, when the measured value by the moisture meter 15 is not within the predetermined range, the valve 17 is opened and the liquid delivering section is operated so that the concentration of water in the cleaning composition in the cleaning tank 11 falls within a predetermined range The cleaning composition in the sub tank 14 and the cleaning composition in the cleaning tank 11 can be circulated through the circulation line 18. [ From the viewpoint of ensuring a high cleaning property for the flux residue, the predetermined range is required to be not less than 2 wt% and not more than 10 wt%, and from the same viewpoint, it is preferably 3 to 8 wt%, more preferably 4 to 7 wt% . The value within a predetermined range is preferably an initial value of the water concentration of the cleaning composition in the cleaning tank 11. [

3, the moisture control mechanism is composed of a circulation line 18 having a sub tank 14, a moisture meter 15, and a valve 17. It is preferable that not only the cleaning tank 11 but also the sub tank 14 is provided with the moisture meter 16. The cleaning device includes a first rinsing tank 12 for pre-rinsing the object to be cleaned in the cleaning tank 11 and a second rinsing tank 13 for performing finish rinsing ) May be further included.

As described above, when water is supplied to the detergent composition used for cleaning the object to be cleaned, the detergent composition can be used for cleaning other objects to be cleaned, which is economical.

(Preliminary cleaning)

In the cleaning method of the present invention, the cleaning step may further include a step of immersing the object to be cleaned in the cleaning agent composition contained in the cleaning tank different from the cleaning tank in which the cleaning step is performed before the first step, for example, the first to fifth steps do. The detergent composition may be the same as the detergent composition to be described later used in the first to fourth steps, or may be a detergent composition for cleaning a conventionally known to-be-cleaned object to which a flux residue is attached other than the detergent composition described later. The immersion time for the detergent composition is preferably, for example, 1 to 10 minutes.

[Rinse process]

The rinsing step is a step of rinsing the contamination of the cleaning agent composition attached to the object to be cleaned, residual flux residue, or re-attached flux residue. When the cleaning method of the present invention does not include both steps 4a and 5 After the fourth step, if the cleaning method of the present invention includes the step 4a but does not include the fifth step, after the step 4a, if the cleaning method of the present invention includes the fifth step, . The rinsing process may be carried out using one rinsing bath or two or more rinsing baths.

The rinsing step can be carried out, for example, by carrying out the same steps as those of the first to fourth steps in the cleaning step, except that the cleaning agent composition is replaced with a rinsing agent composition. That is, in the example of the rinsing step, the object to be cleaned which has undergone the cleaning step is immersed in the rinsing composition contained in the rinsing tank, and then a series of steps including the depressurization step, the depressurization step and the pressure increasing step are carried out in this order. The series of steps may include a step corresponding to step 4a in the cleaning step (pressure holding step after pressure increase). Also in the step 4a of the rinsing step, the cleaning agent composition is changed to the rinsing agent composition, and the same conditions as in step 4a of the cleaning step are used. In addition, in the rinsing step, it is preferable that the cleaning agent composition used in the fifth step in the cleaning step is changed to a rinsing composition and a series of steps including a depressurization step, a depressurization step, and a pressure-increasing step are repeatedly performed, , The pressure reduction step, the pressure reduction step, the pressure reduction step, the pressure reduction step, the pressure reduction step, the pressure reduction step, the pressure reduction step, the pressure reduction step and the pressurization step. Conditions such as temperature, pressure, time, number of cycles, time required for one cycle, ultrasonic vibration, and the like in each process may be the same as those in the cleaning process.

The number of repetitions of the second to fourth steps or the number of repetitions of the second to fourth steps in the rinsing step may be appropriately determined according to the degree of contamination. From the viewpoint of achieving both good rinsing and productivity improvement, More preferably 1 to 40 times, still more preferably 2 to 35 times, still more preferably 3 to 30 times. When a plurality of rinse tanks are used, the total number of times of rinsing performed in each of the rinse tanks may be the above number.

Water, preferably ion-exchanged water or the like is usually used for the rinsing composition. Depending on the degree of contamination, a diluting liquid of a detergent composition obtained by mixing a detergent composition described later and water, preferably ion exchanged water, Is preferably used. When the diluted solution is used as a rinsing composition, the rinsing step includes a rinsing step using a diluting liquid and a finish rinsing step using water, preferably ion-exchanged water, as a rinsing composition. The rinsing process is referred to as a prerin process. The prerin process and the finish rinse process can be carried out by using, for example, the same cleaning bath as that used in the cleaning process as a rinsing bath.

The content of the active ingredient other than water in the detergent composition in the rinse composition used in the prerin process is not particularly limited so long as the contamination and / or detergent composition does not remain in the object to be cleaned after the finish rinse process, More preferably 0.0001 to 8% by weight, and still more preferably 0.0001 to 5% by weight.

The rinsing composition used in the prerin process may contain a detergent composition for cleaning the object to be cleaned with conventionally known flux residue other than the detergent composition described later. The content of water in the rinsing composition, regardless of whether the rinsing agent composition described below or the known cleaning agent composition is contained in the rinsing agent composition, is preferably from the viewpoint of improving the rinsing property of contamination of residual flux residue or reattached flux residue or the like More preferably 90 to 99.9999% by weight, further preferably 92 to 99.9999% by weight, and still more preferably 95 to 99.9999% by weight.

The temperature of the rinsed composition is preferably 50 to 70 ° C from the viewpoint of improving the rinsability.

It is preferable to impart ultrasonic vibration to the rinsing composition from the viewpoint of improving the rinsability in the rinsing process. When the ultrasonic vibration is applied to the rinsing composition in the third step of the rinsing process, since the air existing in the gap through the second step is discharged from the gap, the contamination and rinsing composition can be brought into good contact with each other, The ultrasonic vibration is applied to the deaerated rinsing composition, so that the removability of contamination present in the gap is improved. Therefore, application of the ultrasonic vibration to the rinsing composition in the third step of the rinsing process is preferable because reduction of the rinsing time can be expected. The frequency of the ultrasonic waves and the energy density of the ultrasonic waves may be the same as those given to the cleaning agent composition in the third step.

[Drying process]

In the drying step performed after the rinsing step, for example, the rinsing composition adhered to the surface is removed by blowing warm air into the object to be cleaned, which is taken out from the rinsing composition, and then transported into a vacuum drying vessel. The temperature in the vacuum drying vessel is set to, for example, 50 to 100 DEG C, and the pressure inside the vacuum drying vessel is reduced to 0.1 to 5 (kPa). The drying in the vacuum drying vessel may be carried out for 1 to 30 minutes, for example.

On the other hand, in the cleaning method of the present invention, from the viewpoint of improving the productivity, the rinsing process including the cleaning process, for example, the prerin process and the finishing rinse process, Or a facility including a vacuum drying vessel, at least two pressure-adjustable rinsing vessels, and a vacuum drying vessel. An example of such a facility is disclosed in, for example, Japanese Patent Application Laid-Open No. 6-296940.

[Cleaning Agent Composition]

Next, the cleaning composition used in the cleaning method of the present invention will be described.

The detergent composition in the present invention comprises water (component A), a specific glycol ether (component B) and a specific amine compound (component C).

(Component A)

Component A comprises water such as distilled water, ion exchange water, or ultra pure water.

The content of water in the detergent composition is required to be not less than 2% by weight and not more than 10% by weight from the viewpoint of ensuring high cleaning property for the flux residue. From the same viewpoint, the amount of water is preferably 3 to 8% by weight, more preferably 4 to 7% desirable. The present invention relates to a detergent composition for use in a detergent composition for use in a reduced pressure, a reduced pressure maintained state, and a cleaning method for performing a pressure increase, preferably a reduced pressure, a reduced pressure maintained state, By weight or more and 10% by weight or less. In the present invention, due to the physical force generated due to the pressure change due to the depressurization and the pressure increase, and the physical force generated due to the boiling of the detergent composition during the depressurization holding process, the flux residue in a narrow gap, have. The content of water in the detergent composition is determined by paying attention to the physical force caused by the boiling of the detergent composition. When the content of water is less than 2% by weight, the physical force due to boiling is insufficient. When the content of water exceeds 10% by weight, the solubility of the flux residue is deteriorated.

(Component B)

Component B is composed of a glycol ether represented by the following general formula (1).

R^One-O- (EO)_m-R₂ (One)

R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an oxyethylene group, m represents an average addition mole number of EO, and 2 represents an alkyl group having 1 to 6 carbon atoms. In the general formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms, ? M? 3.

The number of carbon atoms of R ¹ is preferably 2 to 4, more preferably 3 to 4, from the viewpoint of ensuring high cleaning and high safety for flux residues.

Specific examples of the component B represented by the general formula (1) include monoalkyl-type glycol ethers having an average addition molar number (m) of EO of 2, an average of EO A glycol ether of a monoalkyl type having an addition mole number (m) of 3, a dialkyl type glycol ether having an average addition mole number (m) of EO of 2, and a glycol ether of a dialkyl type having an average addition mole number (m) . These glycol ethers may be used alone or in combination of two or more.

Examples of monoalkyl type glycol ethers having an average addition molar number (m) of EO of 2 include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene Glycol monoisobutyl ether, diethylene glycol monohexyl ether, and the like.

Examples of the monoalkyl type glycol ether having an average addition mole number (m) of EO of 3 include triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether and the like. .

Examples of dialkyl glycol ethers having an average addition mole number (m) of EO of 2 include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl propyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Butyl ether, diethylene glycol butyl methyl ether, and diethylene glycol methyl isobutyl ether.

Examples of dialkyl glycol ethers having an average addition mole number (m) of EO of 3 include triethylene glycol dimethyl ether and the like.

Among these glycol ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, Ethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, diethylene glycol butyl methyl ether, diethylene glycol methyl isobutyl ether, And triethylene glycol dimethyl ether are preferable.

The content of the component B in the detergent composition is required to be not less than 50% by weight and less than 97.75% by weight from the viewpoint of improving the cleaning property against the flux residue remaining in a narrow gap. From the same viewpoint, To 97.25% by weight.

(Component C)

Component C is composed of an amine compound represented by the following general formula (2).

In the general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, EO represents an oxyethylene group, p and q each represent an average addition mole number of EO, and 1? P + Satisfies.

The carbon number of R &lt; ³ &gt; is preferably 1 to 3 from the viewpoints of cleaning property of the flux residue remaining in the gap and improvement of the rinsability. p + q satisfies 1? p + q? 4, and it is more preferable that 1? p + q? 3 is satisfied from the viewpoint of improving the cleaning property of the flux residue remaining in the gap.

Specific examples of the component C represented by the general formula (2) include monoethanolamine, diethanolamine, methyldiethanolamine, methylmonoethanolamine, methyldiethanolamine and methylmethanolamine, from the viewpoints of improving the rinsability and improving the cleaning property of the flux residue remaining in the gaps. And alkylolamines such as ethanolamine, ethylmonoethanolamine and the like are preferable.

The content of the component C in the detergent composition is required to be not less than 0.05% by weight and not more than 5% by weight, preferably 0.5 to 1.5% by weight, from the viewpoints of improving the rinsability and improving the cleaning property of the flux residue remaining in the crevice.

The weight ratio (component B / component C) of the component B and the component C is preferably 20 to 99, more preferably 94 to 98, and more preferably 95 to 97 in terms of improving the cleaning property of the flux residue remaining in the gap desirable.

The weight ratio (component B / component A) of the component B and the component A is preferably 20 to 99, more preferably 20 to 50, and more preferably 30 to 50 in view of improvement in cleaning property against the flux residue remaining in the gap desirable.

It is preferable that the weight ratio of the weight of the component B and the total weight of the component A and the component C (component B / [component A + component C]] is 10 to 50 from the viewpoint of improving the cleaning property of the flux residue remaining in the gap, More preferably from 15 to 35, and still more preferably from 23 to 33.

The detergent composition may also contain the following surfactants (component D).

The content of the component D in the detergent composition is preferably less than 0.01% by weight from the viewpoint of suppressing the foaming property, more preferably 0.005% by weight or less, more preferably substantially not including 0.005% by weight or less .

Specific examples of the component D include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene carboxylic acid ester, polyoxyethylene polyoxypropylene carboxylic acid ester, polyoxyethylene polyoxypropylene copolymer, etc. Non-ionic surfactants of the following formula (1).

[Other optional ingredients]

The detergent composition can be used as a detergent composition in the range of not deteriorating the high cleaning property against the flux residue present in a narrow gap, good rinsing property by water, and low foamability, which is exhibited when the object to be cleaned is cleaned using the detergent composition, Amine compounds other than C include morpholines such as morpholine and ethyl morpholine; Piperazine, triethylamine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, and the like.

The detergent composition includes, as other components, a group consisting of a chelating agent, a preservative, a corrosion inhibitor, a bactericide, an antibacterial agent, an antioxidant, an ester, and alcohols such as glycerin and polyethylene glycol, which are usually used in a detergent composition , And the like.

The total content of the other optional components in the detergent composition is preferably 45% by weight or less, more preferably 20% by weight or less, still more preferably 0.1% by weight or less from the viewpoint of improvement in cleaning property against the flux residue remaining in the gap , And even more preferably 0.05% by weight or less.

[Method of preparing detergent composition]

The method of preparing the detergent composition is not particularly limited and may be prepared by mixing component A, component B, and component C, and further mixing component D and / or other optional components as needed.

As the container for mixing the respective components, a container made of SUS, a container made of GS (glass lining), or the like can be used, and as the solution stirring means, a propeller blade, a pitched paddle, a max blend, Or a magnetic stirrer or the like may be used.

The temperature of the mixed liquid during stirring is preferably 10 to 40 占 폚, more preferably 20 to 30 占 폚. The peripheral speed of the stirring vane is usually 1 to 3 m / sec. Further, it is preferable to mix the mixture for 15 minutes or longer after the entire components are put into the container, and it is more preferable to mix the mixture for 20 minutes or longer.

[PH of detergent composition]

The pH of the detergent composition may be suitably determined according to the type of the object to be cleaned, required quality of the object to be cleaned after cleaning, etc., and is preferably 8 to 11, more preferably 9 to 11 from the viewpoint of suppressing corrosion of the object to be cleaned.

The pH of the detergent composition may be adjusted depending on the necessity, if necessary, by using an inorganic acid such as nitric acid or sulfuric acid, an organic acid such as an oxycarboxylic acid, a polyvalent carboxylic acid, an aminopolycarboxylic acid or an amino acid and a metal salt or an ammonium salt thereof, ammonia, sodium hydroxide, Amines and the like can be appropriately adjusted to the desired amount.

[Manufacturing method of electronic parts]

A manufacturing method of an electronic component according to the present invention is a manufacturing method of an electronic component including a solder bump, comprising the steps of: forming a solder bump on a substrate of an electronic component using a solder flux; Of the flux residue. That is, in the method of manufacturing an electronic component of the present invention, a component is soldered on a substrate using a solder flux, and then reflowed to form a manufacturing intermediate product (object to be cleaned) on which the component is mounted And a step of cleaning the flux residue derived from the solder flux existing in the gap between the substrate and the component by the cleaning method of the present invention. The solder bumps are formed by, for example, a printing method in which paste-like solder flux is printed on a substrate and then heated (reflowed) to form solder bumps, or an electric solder plating is applied to the opening of the resist layer formed on the substrate A method of forming a solder bump by filling a paste-like solder flux into an opening of a resist layer formed on a substrate and then heating (reflowing) the solder bump by heating (reflowing) And can be formed by a solder bump forming method using a conventionally known flux.

Here, the term "substrate" of an electronic component includes a semiconductor chip and the like on which a solder bump can be formed, in addition to a circuit board, a package substrate (interposer), and the electronic component includes a semiconductor device including the substrate. Examples of the "part" include a semiconductor chip, a chip type capacitor, and a circuit board different from the circuit board used as the "board ". Whatever method the solder bump is formed, the flux residue in the space (gap) between the substrate and the component can be efficiently cleaned by cleaning the substrate or the like with the cleaning method of the present invention after the reflow process. When the cleaning method of the present invention is employed, for example, flux residues in a narrow gap having a height of 5 to 500 mu m, a width of 130 to 20,000 mu m, and a depth of 130 to 25000 mu m, Can be easily removed.

Example

The compositions of Examples 1 to 17 and Comparative Examples 1 to 23 were obtained by blending and mixing the respective components so as to obtain the compositions shown in Tables 1, 3, 5, and 6. The temperature of the mixed liquid during stirring was 25 DEG C, and a magnetic stirrer (80 mm rotator) was used for stirring the mixed liquid. The number of revolutions of the magnetic stirrer was 200 rpm, and the stirring time after putting all the components into the container was 30 minutes. The pH of these detergent compositions was 10-11. The pH of each detergent composition was measured at 25 占 폚 using a pH meter (HM-30G manufactured by Toaden Pako Co., Ltd.).

The following tests (1) to (6) were carried out using the obtained detergent composition. The cleaning composition thus obtained was charged in a washing tank (volume: 25 L) and heated to 60 캜.

<Preparation of flux residue>

Cream solder (LIFSOLDER LF-204-11 manufactured by Tamura Kaken Co., Ltd.) was coated on a copper plate and then subjected to heat treatment (250 캜) in a nitrogen atmosphere to prepare a flux residue. That is, by melting the flux in the cream solder by the heat treatment, the solder metal and the flux residue were separated by causing the solder metal to float. Flux residue can be observed on the copper plate as contamination like brown film.

<Preparation of Test Piece>

1A and 1B, a pair of aluminum plates 2 are placed on one main surface of a PKG substrate 1 of a commercially available MPU (micro processing unit) so that the interval W4 is 3 mm. And the cover glass 5 was disposed on the pair of aluminum plates 2. The cover glass 5 was placed on the pair of aluminum plates 2, The height W3 of the space between the cover glass 5 and the PKG substrate 1 is 50 mu m. The epoxy resin 3a is used to fix the pair of aluminum plates 2 to the PKG substrate 1 and to fix the cover glass 5 to the pair of aluminum plates 2, A gap 17 surrounded by the substrate 1, the pair of aluminum plates 2, and the cover glass 5 was formed.

The flux residue prepared in the above &quot; Preparation of flux residue &quot; was taken from the copper plate and placed in the vicinity of one end of the gap 17 in an amount of 0.05 g, and then placed in a high-temperature bath at 150 ° C. Then, the flux residue penetrated into the gap (17) by the capillary phenomenon. Then, one end of the gap 17 was sealed with an epoxy resin 3b to obtain a test piece. On the other hand, the longitudinal length of the flux residue filled in the region 4 by the capillary phenomenon was 5 mm, and the entire surface surrounding the region 4 was covered with the flux residue. In Fig. 1A, the lengths of W1 and W2 are all 5 mm, and the reference numeral 6 denotes air stacked with air. The space (gap 17) surrounded by the PKG substrate 1, the pair of aluminum plates 2, the cover glass 5 and the epoxy resin 3b has a height of 50 m, a width of 3 mm and a depth of 10 mm.

(1) Clearance test 1

Next, the test piece was set in the jig and immersed in a detergent composition (60 DEG C, 5L) in a washing tank (volume: 25L) such that the air bubble 6 was below the area 4. [ Subsequently, the pressure in the washing tank is reduced at a speed of, for example, 19 kPa / s (in the case of Example 1) until the pressure P ₁ shown in Tables 1, 3, 5 and 6 is reached After the roughing, the decompressed pressure is maintained for the time shown in Tables 1, 3, 5 and 6 (see "Decompression Holding Time") and then the pressure in the cleaning tank is increased to 19 kPa / s 1), the pressure was increased until the pressure P ₂ shown in Tables 1, 3, 5, and 6 was reached. If the pressure P ₂ is equal to the atmospheric pressure (101.3 (kPa)), then the pressure in the washing tank is maintained at the normal pressure for the time shown in Table 1, Table 3, Table 5 and Table 6 Respectively. When the pressure P ₂ is lower than the normal pressure, the pressure in the cleaning tank is maintained for the time shown in Table 1, Table 3, Table 5, and Table 6 (see "pressure holding time after pressure increase"). The series of steps consisting of the depressurization step, the depressurization step, the step-up step, and the step of maintaining the pressure after the step-up was performed as many times as shown in Tables 1, 3, 5 and 6 (see "Number of cycles"). In Comparative Example 1, neither the decompression nor the boosting was performed. In addition, the pressure holding step after elevated pressure was not carried out for Examples 16 to 17 and Comparative Examples 2 and 20 to 23. In Comparative Example 13, the reduced pressure holding step and the pressure holding step after the pressure increase were not performed.

The depressurization rate and the pressure increase rate are obtained by dividing the pressure difference between the initial pressure in each process and the initial pressure (predetermined pressure) in the next process by the time required for obtaining the predetermined pressure. For example, in Example 1, since the pressure was reduced from the atmospheric pressure (101.3 kPa) to 4.0 kPa in only 5 seconds, the pressure reduction rate became 19 kPa / s (= (101.3-4.0) / 5).

The pressure in the washing tank during the depressurization process, the depressurization maintaining process, the pressure increasing process, and the pressure maintaining process after the pressure increase was measured with a manometer (DM-10S manufactured by Shibata Kagaku Co., Ltd.). The pressure in the washing tank was continuously monitored during each process. In all the examples and comparative examples in which the depressurization maintaining step and the pressure maintaining step after the pressure increasing step were carried out, the pressure in the cleaning tank in the reduced pressure holding step was within the range of P ₁ ± 0.4 (kPa) The pressure in the tank was within the range of P ₂ ± 0.4 (kPa).

The temperature of the detergent composition in the washing tank in the depressurization step, the depressurization maintaining step, the pressure increasing step, and the pressure holding step after the pressure increasing step and the temperature of the rinsing composition described later were measured with a thermometer attached to the cleaning tank. The temperature of the detergent composition in the depressurization process, the depressurization maintaining process, the pressure increasing process, and the pressure maintaining process after pressure increasing was measured and monitored every one second in each process. In all of the Examples and Comparative Examples, I was in. For example, the temperature "60 占 폚" of the detergent composition of Example 1 in Table 1 is determined by a pressure reducing step (second step), a depressurization maintaining step (third step), a pressure increasing step (fourth step) (Step 4a), the average value of the temperature of the detergent composition is 60 DEG C in all the steps. On the other hand, the temperature control of the cleaning agent composition during the depressurization step, the depressurization step, the step-up step, and the pressure holding step after the depressurization step was controlled at a designated temperature by monitoring the temperature every one second by the temperature control device provided in the cleaning tank.

Thereafter, a pre-rinse process and a finishing rinse process were performed once in this order, and the cleaned object washed after the finish rinse process was dried. The cleaning process, the prerin process, and the finish rinse process were carried out in different tanks, respectively.

In each of the examples and comparative examples, a 5% diluent of the detergent composition used was used as the rinse composition in the prerin process, and the depressurization step, the depressurization step, the pressure step, The process was carried out in this order. The number of cycles is the same as that of the corresponding cleaning process.

In the finishing rinse step, the depressurization step, the depressurization step, the pressure increasing step, and the pressure maintaining step after the pressure increase step were performed in the same order as the corresponding cleaning step, except that water was used as the rinsing composition. The number of cycles is the same as that of the corresponding cleaning process.

Also in the prerin process and the finish rinse process, neither the decompression nor the boosting was performed in Comparative Example 1. In addition, the pressure holding step after the pressure increase was not carried out for Examples 16 to 17 and Comparative Examples 2 and 20 to 23. In Comparative Example 13, the depressurization maintaining step and the pressure maintaining step after the pressure increase were not performed.

Drying of the test pieces after the rinsing process and the rinsing process was performed by removing the rinsing composition adhering to the surface by blowing warm air (25 DEG C) on the test pieces and then leaving the test pieces in a vacuum drying container set at 80 DEG C for 5 minutes Respectively. The pressure in the vacuum drying vessel was 1.0 (kPa).

During the cleansing composition of Examples 1 to 13, 16 and 17 and the cleaning compositions of Comparative Examples 1 to 13 and 20 to 23 in the cleansing test 1, while the test piece was immersed in the cleaning composition, ultrasonic vibration (40 kHz, 1.0 W / Cm &lt; 2 &gt;) was continuously applied.

(2) Clearance test 2 (a)

The same tests as in the cleansing test 1 were conducted except that the energy density of the ultrasonic vibration applied to the cleaning composition was 0.5 W / cm 2. On the other hand, the clearance cleaning test 2 (a) was carried out on the cleaning compositions of Examples 1 to 13 and the cleaning compositions of Comparative Examples 1 to 13.

(3) Clearance test 2 (b)

The same test as in the gap cleansing test 2 (a) was performed except that the number of cycles in the cleaning process was twice that in the clearance cleaning test 2 (a). On the other hand, the clearance cleaning test 2 (b) was carried out on the detergent compositions of Examples 1 to 13 and the detergent compositions of Comparative Examples 1 to 13.

The area of the region where the flux residue remained in the region (4) visible when the test pieces before and after each clearance cleaning test were viewed in plan was observed using an optical microscope (magnification: 50 times). The percentage of the area of the area of the area 4 where the flux residue is removed is calculated as the cleaning rate (percentage) with respect to the area of the area 4 seen when the test pieces are viewed in a plane, The cleanability of the detergent composition for the residue was evaluated.

(4) Clearance test 3

The cleaning compositions of Examples 14 to 15 and the cleaning compositions of Comparative Examples 14 to 19 were tested in the same manner as the cleansing test 1 except that ultrasonic vibration was not applied. In Comparative Example 14, neither the decompression nor the boosting was performed. The pressure holding step after the pressure increase was not carried out for Examples 14 and 15 and Comparative Examples 15 to 19.

(5) Clearance Test 4 (Example 18: Adjustment of Water Concentration in Cleaning Agent Composition)

As shown in Fig. 3, this test includes a cleaning tank 11, a first rinsing tank 12, and a second rinsing tank 13, which are subjected to a finishing rinse process, A cleaning device was used. In addition, 20 test pieces prepared in the same manner as in < preparation of test pieces > were prepared.

After setting one of the 20 test pieces to the jig, the test piece was placed in a cleaning agent composition (60 DEG C) in the cleaning tank 11 so that the air jig 6 (see Fig. 1A) ). The detergent composition of Example 1 was used as the detergent composition.

The depressurization step, the depressurization maintaining step, the pressure increasing step, and the pressure maintaining step after the pressure increase were carried out in this order under the same conditions as the above (1) clearance cleaning test (1). That is, the inside of the cleaning tank was decompressed to 4 kPa, the reduced pressure state was maintained for 10 seconds, the pressure in the cleaning tank was increased to the normal pressure (101.3 kPa), and then the normal pressure state was maintained for 10 seconds. This series of steps consisting of the depressurization step, the depressurization maintaining step, the pressure increasing step, and the pressure maintaining step after the pressure increasing step was repeated 10 times. The amount of the cleaning agent composition in the cleaning tank before the initiation of the cleaning process was 20L. One cycle consisting of the depressurization step, the depressurization maintaining step, and the pressure increasing step and the pressure holding step after the pressure increasing step was performed for 30 seconds. The cleaning time is 300 seconds.

While the test piece was immersed in the cleaning composition, ultrasonic vibration (40 kHz, 1.0 W / cm 2) was continuously applied to the cleaning composition.

A series of steps consisting of a depressurization step, a depressurization maintaining step, a pressure increasing step, and a pressure holding step after the pressure increasing step were repeated 10 times, and the test pieces were taken out from the cleaning tank. The test pieces were subjected to a flour rinse and a finish rinse in the same manner as in the above (1) Clear Cleansing Test (1) once in this order. After the finish rinse process, the cleaned test pieces were dried. The prerin process and the finish rinse process were performed for 300 seconds each. In the prerin process, a 5% diluent of the detergent composition of Example 1 was used as the rinse composition, and water was used as the rinse composition in the finish rinse process.

Next, the detergent composition in the cleaning tank 11 and the detergent composition in the sub tank 14 are circulated before the test piece (second chapter) different from the test piece is introduced into the cleaning tank, and the detergent composition in the cleaning tank 11 The content of water in the composition was adjusted to the same concentration as the initial value (5.0 wt%).

The water content of the detergent composition in the cleaning tank 11 and the water content in the detergent composition in the sub tank 14 are both measured using a water content meter (EMC-113N manufactured by Yamamoto Denki Instruments) (15, 16) Respectively. The prerin process and the finish rinse process were carried out at each termination of the rinse of one test piece with the composition of the unused rinse. This cleansing test was carried out in the same manner up to the second chapter of the test piece. The number of cleaning cycles for each test piece is 10, and the total number of cycles for a total of 20 test pieces is 200.

On the other hand, as a reference example, the same cleaning property test was performed on 20 test pieces in the same manner as in Example 18, except that the water content in the cleaning agent composition was not adjusted in the cleaning property test. The results of this cleaning test are shown in Table 7.

As can be seen from Table 7, when the water content in the detergent composition is 2 to 10% by weight, high cleaning property can be obtained. Also, when the detergent composition is repeatedly used, it is possible to maintain high cleaning performance by replenishing the evaporated water according to use and keeping the water content in the detergent composition at 2 to 10% by weight.

(6) Evaluation of cleaning property

&Lt; Judgment Criteria of Flux Residue Cleaning >

A: 90% or more cleaning rate

B: Washing rate is 80% or more and less than 90%

C: Cleaning rate is 70% or more and less than 80%

D: Cleaning rate is 60% or more and less than 70%

E: Washing rate is 50% or more and less than 60%

F: Less than 50% cleaning rate

(7) Rinsing property test

In the rinsability test, it was tested to what extent the cleaning composition contained in the gap 17 between the pair of glass plates in the test piece could be rinsed with water. However, the test piece used in this test was not filled with the flux residue in the gap 17.

A test piece filled with the detergent composition colored by the water-soluble dye methylene blue (reagent; Sigma Aldrich) was prepared as the gap 17. A test piece was set in the jig such that the end portion of the pair of glass plates, which was away from the epoxy resin 3b in the longitudinal direction, was downward, and the test piece was immersed in the rinse composition (water, 60 ° C) . In the water rinsability test, the detergent composition was changed to water and rinsed under the same conditions as the cleaning process (first to fifth processes) in the interstitial cleaning test 1 or 3.

The area of the region where the dyes remain visible when the clearance 17 of the test piece after the rinsing property test was seen in a plane was observed using an optical microscope (magnification: 50 times). (Percent) of the area of the area where the dye is removed in a plane viewed when the gap 17 of the test piece is viewed in plan, with respect to the area of the plane seen when the gap 17 of the test piece is viewed in plan, , And the rinsability of the cleaning composition was evaluated according to the following criteria.

&Lt; Criteria of Rinseability of Water in Cleaning Agent Composition >

A: Rinsing property is 90% or more

B: Rinsing property is 70% or more and less than 90%

C: Rinsing property is 50% or more and less than 70%

D: Less than 50% rinsability

(8) Foaming test at ultrasonic vacuum pulse cleaning

(a) The height of the foam when 2 liters of the detergent composition is placed in the container 7 shown in Fig. 2 and the pressure inside the container 7 is reduced (5 kPa), (b) 2 liters of a diluent (corresponding to a rinse composition for a princess process) obtained by diluting the detergent composition with water so that the concentration of the composition was 10% by weight and the height of the foam when the inside of the container 7 was reduced (5 kPa) Respectively.

In FIG. 2, reference numeral 8 denotes a pressure reducing valve, reference numeral 10 denotes a valve that controls opening and closing of a pipe connected to a vacuum pump, and reference numeral 9 denotes a liquid drain valve.

&Lt; Criteria for determination of foaming property upon ultrasonic vacuum pulse cleaning >

A: Bubble height less than 10cm

B: The foam height is 10 cm or more and less than 20 cm

C: Bubble height of 20cm or more

Table 1 - As shown in Table 6, the content of water as a detergent composition has been used to a small specific composition in 2-10 wt%, P in a range of three is 0.1 ~ 7kPa pressure in the tank to reach in a vacuum process ₁ (kPa), the pressure in the cleaning tank in the reduced pressure holding step is P ₁ ± 0.4 (kPa), the temperature of the detergent composition is maintained at 50 to 70 ° C for 8 to 16 seconds, embodiment the pressure in conducts to voltage step-up process from a P ₂ (kPa) in the range of 50 ~ 120kPa, depressurization process 10-220 seconds in the tank examples 1 to 17 is a narrow gap than that of the comparative examples 1 to 23, the width ( 17), the cleaning property of the cleaning agent composition is high and the rinsing property by water is good. In addition, the detergent compositions of Examples 1 to 17 contain 0.008 wt% or less of the surfactant other than the components B and C, and substantially do not contain surfactants other than the components B and C, so that the air bubbles are suppressed.

The details of each component in Table 1, Table 3, Table 5, and Table 6 are as follows.

[Component B]

Diethylene glycol monobutyl ether (manufactured by Nippon Yuka Co., Ltd.)

Triethylene glycol monobutyl ether (manufactured by Nippon Yuka Co., Ltd.)

Diethylene glycol monohexyl ether (manufactured by Nippon Yuka Co., Ltd.)

Triethylene glycol dimethyl ether (manufactured by Nippon Yuka Co., Ltd.)

[Component C]

Diethanolamine (product of Wako Pure Chemical Industries, Ltd.)

Methyldiethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.)

[Component D]

SecC _{12 -14-} O- (EO) ₇ H (nonionic surfactant, manufactured by Nihon Shokubai Co., Ltd.)

SecC _{12 -14-} O- (EO) ₇ H is a mixture of SecC ₁₂ -O- (EO) ₇ H and SecC ₁₄ -O- (EO) ₇ H.

[Optional ingredients]

Glycerin (manufactured by Kao Corporation)

[Other]

Solvent naphtha (manufactured by Wako Pure Chemical Industries, Ltd.)

Surfactant 10% aqueous solution: Lutensol XL-70 (10 wt% aqueous solution of nonionic surfactant)

The detergent composition of the present invention can be suitably used for cleaning flux residues remaining in narrow gaps.

Claims (11)

And a cleaning step of cleaning the to-be-cleaned object to which the flux residue is attached using the cleaning agent composition,
In the cleaning step,
An immersion step (first step) of immersing the object to be cleaned with the flux residue in the cleaning composition contained in a pressure-adjustable cleaning tank,
(Second step) of reducing the pressure in the cleaning bath to a pressure P ₁ (kPa) satisfying the following formula (1) to boil the water contained in the cleaning composition,
0.1 (kPa)? P _1? 7 (kPa) (1)
The pressure in the cleaning tank depressurized in the depressurization step is maintained at P ₁ ± 0.4 (kPa), and the temperature of the detergent composition in the cleaning tank is maintained at 50 to 70 ° C for 8 to 16 seconds, (Third step) for maintaining the state of the pressure reduction,
(Fourth step) in which the pressure in the cleaning tank after the reduced-pressure holding step is set to a pressure P ₂ (kPa) satisfying the following formula (2)
_{50 (kPa) ≤P 2 ≤120 (} kPa) (2)
The second to fourth steps are carried out for 10 to 220 seconds,
The detergent composition comprises
2 to 10% by weight of water (component A)
50% by weight or more but less than 97.75% by weight of glycol ether (component B)
(Component C) in an amount of not less than 0.05 wt% and not more than 5 wt%
The component B is represented by the following general formula (1)
R ¹ -O- (EO) _m -R ² (1)
Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO is an oxyethylene group, m is an average addition mole number of EO, m? 3.]
Wherein the component C is represented by the following general formula (2).
[Chemical Formula 1]

[Wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, EO represents an oxyethylene group, p and q each represent an average addition mole number of EO, and 1 p + q 4 . The method according to claim 1,
Further comprising repeating at least the second step to the fourth step 1 to 50 times (fifth step)
And the second step to the fourth step, which are repeated in the fifth step, are carried out for 10 to 220 seconds, respectively. The method according to claim 1,
Pressure holding step (step 4a) for holding the pressure in the cleaning tank at a pressure within a range of 50 to 120 kPa for 8 to 16 seconds at P ₂ ± 0.4 (kPa) after the fourth step And a cleaning step of cleaning the object to be cleaned. 3. The method of claim 2,
And a rinsing step of rinsing the object to be cleaned with a rinsing composition containing 90 to 99.9999% by weight of water. 5. The method of claim 4,
Wherein the rinsing step is carried out by replacing the detergent composition used in the second step to the fourth step with the rinsing composition in the fifth step. The method according to claim 1,
Wherein the third step of the cleaning step is carried out while applying ultrasonic vibration to the cleaning agent composition. 6. The method of claim 5,
Wherein the third step of the rinsing step is carried out while applying ultrasonic vibration to the rinsing composition. A step of forming a solder bump on a substrate of an electronic component by using a solder flux including flux;
And a step of cleaning the flux residue derived from the flux by the cleaning method of the object to be cleaned according to claim 1. A cleaning apparatus used in a cleaning method of the object to be cleaned according to claim 1,
And a moisture control mechanism for reducing the content of the water (component A) in the detergent composition in the cleaning tank to 2 wt% or more and 10 wt% or less. 3. The method of claim 2,
Pressure holding step (step 4a) for holding the pressure in the cleaning tank at a pressure within a range of 50 to 120 kPa for 8 to 16 seconds at P ₂ ± 0.4 (kPa) after the fourth step And a cleaning step of cleaning the object to be cleaned. 3. The method of claim 2,
Wherein the third step of the cleaning step is carried out while applying ultrasonic vibration to the cleaning agent composition.

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